purified by column chromatography on silica gel
(n-hexane/EtOAc, 20:1) to obtain the compound 2’ as a
colorless oil. Yield, 317 mg (5.81 mmol), 53%; 1H NMR (500 MHz,
CDCl3) δ 0.88 (9H, t, J = 7.1 Hz), 1.27−1.39 (25H, m), 1.41−1.47 (5H,
m), 1.79 (6H, quin, J = 7.9 Hz), 4.37 (6H, t, J = 6.7 Hz), 8.84 (3H, s);
13C NMR (125 MHz, CDCl3) δ 14.1, 22.6, 25.9, 28.6, 29.16, 29.20,
31.8, 65.8, 131.5, 134.4, 165.1; IR (ATR, cm−1) ṽ = 723, 741, 779, 870,
957, 972, 1009, 1132, 1142, 1198, 1233, 1294, 1327, 1369, 1443, 1609,
1738, 1751, 2853, 2928; HRMS (FAB+): m/z calcd for C33H55O6:
547.3999; found: 546.3999.
4.3. Synthesis.
Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl)
isophthalate (1m). Dimethylaminopyridine (DMAP) (36.1 mg,
0.30 mmol) was slowly added to a stirred solution of
1H,1H-pentadecafuluoro-1-octanol (1.74 g, 2.69 mmol) in
toluene (10 mL) at room temperature under N2. After 10 min,
isophthaloyl chloride (229 mg, 1.13 mmol) and Et3N (5 mL)
were added in sequence and stirred at 100°C for 48 h. The
mixture was then cooled to room temperature and the volatile
materials were removed under reduced pressure, dissolved in
CH2Cl2 (30 mL), and washed several times with H2O. The
crude material was purified by column chromatography on
silica gel (n-hexane/EtOAc, 1:20) to obtain the compound 1m
as a white solid. Yield, 530 mg (0.570 mmol), 50%; mp,
65.0−66.0°C; 1H NMR (500 MHz, CDCl3) δ 4.85 (4H, t, J = 13.0 Hz),
7.64 (1H, t, J = 7.9 Hz), 8.32 (2H, dd,J = 1.8 and 7.9 Hz), 8.73 (1H, t, J
= 1.6 Hz); IR (ATR, cm−1) ṽ = 723, 781, 957, 989, 1007, 1103, 1140,
1196, 1229, 1296, 1325, 1369, 1443, 1611, 1738, 1751; HRMS
(FAB+): m/z calcd for C24H9F30O4: 931.0022; found: 931.0018 [(M +
H)+].
4.4. Methods. In a typical procedure, the weighed sample was
mixed with the specified solvent in a sealed sample tube, and
then the mixture was heated until the solid was completely
dissolved. The resulting solution (concentration 10.0% (w/v))
was cooled to 5 °C for 10 min, and finally the test tube was
inverted to determine whether the sample inside could still flow.
Gelation was considered to have occurred when
a
homogeneous substance was obtained and exhibited no
gravitational flow. In such cases, the sample was denoted as ‘G’
(gel). In other cases, solution and gel might coexist in a system;
these samples were denoted as ‘PG’ (partial gel). Systems in
which only the solution remained were denoted as ‘S’
(solution). The label ‘P’ (precipitation) was used for systems in
which a precipitate was obtained at the end of the tests. Finally,
systems in which the samples could not be dissolved, even at
the boiling point of the solvent, were denoted as ‘I’ (insoluble).
Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl)
terephthalate (1p).51 DMAP (35.2 mg, 0.28 mmol) was slowly
added
to
a
stirred
solution
of
1H,1H-pentadecafuluoro-1-octanol (1.85 g, 2.69 mmol) in
toluene (10 mL) at room temperature under N2. After 10 min,
terephthaloyl chloride (224 mg, 1.10 mmol) and Et3N (5 mL)
were added in sequence and stirred at 100 °C for 48 h. The
mixture was then cooled to room temperature and the volatile
materials were removed under reduced pressure, dissolved in
CH2Cl2 (30 mL), and washed several times with H2O. The
crude material was purified by column chromatography on
silica gel (n-hexane/CH2Cl2, 3:1) to obtain the compound 1p as
a white solid. Yield, 375 mg (0.403 mmol), 37%; mp, 66.5−67.5°C;
1H NMR (500 MHz, CDCl3) δ 4.86 (4H, t, J = 16.8 Hz), 8.17 (4H, s);
IR (ATR, cm−1) ṽ = 719, 874, 966, 988, 1016, 1034, 1103, 1138, 1200,
1325, 1369, 1400, 1452, 1732; HRMS (FAB+): m/z calcd for
C24H9F30O4: 931.0022; found: 931.0052 [(M + H)+].
Acknowledgements
This work was supported by the Grant-in-Aid for Young
Scientists (B) from JSPS (Grant Number 17K14452). We thank
Mr. Kaito Sugane of Chiba Institute of Technology for the
XRD measurements.
5. References and notes.
1.
Part 2 of ‘‘C3-symmetric gelators without hydrogen bond
moiety.’’ For Part 1, see: T. Shimasaki, Y. Okamiya, R.
Sato, K. Hara, T. Nakamura, N. Teramoto, M. Shibata
Tetrahedron, 2016, 72, 1517−1523.
Tris(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl)
benzene-1,3,5-tricarboxylate (2). DMAP (41.3 mg, 0.34
2.
3.
4.
5.
6.
7.
8.
9.
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mmol) was slowly added to
a
stirred solution of
1H,1H-pentadecafuluoro-1-octanol (2.67 g, 6.68 mmol) in
acetonitrile (5 mL) and hexafluorobenzene (1 mL) at room
temperature under N2. After 10 min, benzene-1,3,5-tricarbonyl
trichloride (522 mg, 1.97 mmol) and Et3N (10 mL) were added
in sequence and stirred at 80 °C for 120 h. The mixture was
then cooled to room temperature and the volatile materials were
removed under reduced pressure, and added to CH2Cl2 (30 mL).
The white powder, which was insoluble in CH2Cl2, was
collected by filtration, and washed with CH2Cl2, acetonitrile,
and H2O several times to obtain the compound 2 as a white
1
solid. Yield, 953 mg (0.70 mmol), 36%; mp, 114.5.0−115.5°C; H
NMR (500 MHz, CDCl3 in the presence of hexafluorobenzene) δ 4.98
(6H, t, J = 13.0 Hz), 9.01 (3H, s); IR (ATR, cm−1) ṽ = 723, 779, 870,
959, 974, 1009, 1103, 1142, 1198, 1231, 1296, 1327, 1443, 1611, 1737,
1751; HRMS (FAB+): m/z calcd for C33H10F45O6: 1356.9759; found:
1356.9743 [(M + H)+].
Trioctyl benzene-1,3,5-tricarboxylate (2’). DMAP (37.0 mg,
0.30 mmol) was slowly added to a stirred solution of 1-octanol
(861 mg, 6.61 mmol) in toluene (5 mL) at room temperature
under N2. After 10 min, benzene-1,3,5-tricarbonyl trichloride
(290 mg, 1.09 mmol) and Et3N (5 mL) were added in sequence
and stirred at 100 °C for 72 h. The mixture was then cooled to
room temperature and the volatile materials were removed
under reduced pressure, dissolved in CH2Cl2 (30 mL), and
washed several times with H2O. The crude material was
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